Recent Methodologies That Exploit Oxidative Addition of C–N Bonds to Transition Metals DOI
Javier García‐Cárceles, Karim A. Bahou, John F. Bower

и другие.

ACS Catalysis, Год журнала: 2020, Номер 10(21), С. 12738 - 12759

Опубликована: Окт. 19, 2020

The activation of σ-bonds by transition metals underpins a wide range methods for the synthesis complex molecules. Within this context, C–N bond has emerged recently as powerful strategy preparation or utilization nitrogen-containing compounds, due to prevalence bonds in organic compounds. A key challenge area is that most are relatively inert, and makes their difficult task. Since turn millennium number published articles regarding grown exponentially, providing important improvements methodologies such transformations. Indeed, several distinct strategies have been developed achieve activation. common exploited either strain release quaternization nitrogen center, while other state-of-the-art strategies, oxidative addition neutral use directing groups, also appeared. Despite considerable progress, deeper insight into mechanisms atom economy still required field advance. In Perspective we give an overview advances catalytic where achieved metals.

Язык: Английский

Nickel-Catalyzed Dicarbofunctionalization of Alkenes DOI

Xiaoxu Qi,

Tianning Diao

ACS Catalysis, Год журнала: 2020, Номер 10(15), С. 8542 - 8556

Опубликована: Июль 2, 2020

1,2-Dicarbofunctionalization of alkenes has emerged as an efficient synthetic strategy for preparing substituted molecules by coupling readily available with electrophiles and/or nucleophiles. Nickel complexes serve effective catalysts owing to their tendency undergo facile oxidative addition and slow β-hydride elimination, capability access both two-electron radical pathways. Two-component alkene functionalization reactions have achieved high chemo-, regio-, stereoselectivities tethering one the partners substrate. Three-component reactions, however, often incorporate directing groups control selectivity. Only a few examples directing-group-free difunctionalizations unactivated been reported. Therefore, great opportunities exist development three-component difunctionalization broad substrate scopes tunable stereoselectivities.

Язык: Английский

Процитировано

384
Pyridinium Salts as Redox‐Active Functional Group Transfer Reagents DOI
Simon L. Rössler, Benson J. Jelier, Emmanuel Magnier

и другие.

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(24), С. 9264 - 9280

Опубликована: Окт. 10, 2019

Abstract In this Review, we highlight recent advances in the understanding and design of N‐functionalized pyridinium scaffolds as redox‐active, single‐electron, functional group transfer reagents. We provide a selection representative methods that demonstrate reactivity fundamental emerging field. The these reagents can be divided into two divergent pathways: homolytic fragmentation to liberate N‐bound substituent corresponding radical or an alternative heterolytic liberates N‐centered radical. A short description elementary steps involved induced by single‐electron is also critically discussed guide readers towards processes thought occur under conditions.

Язык: Английский

Процитировано

257
Nickel-Catalyzed Enantioconvergent Reductive Hydroalkylation of Olefins with α-Heteroatom Phosphorus or Sulfur Alkyl Electrophiles DOI

Shi-Jiang He,

Jia‐Wang Wang, Yan Li

и другие.

Journal of the American Chemical Society, Год журнала: 2019, Номер 142(1), С. 214 - 221

Опубликована: Дек. 15, 2019

Substantial advances in enantioconvergent C(sp3)–C(sp3) bond formation reactions have been made recent years through the use of transition-metal-catalyzed cross-coupling racemic secondary alkyl electrophiles with organometallic reagents. Herein, we report a general process for asymmetric construction alkyl–alkyl bonds adjacent to heteroatoms, namely, nickel-catalyzed reductive hydroalkylation olefins α-heteroatom phosphorus or sulfur electrophiles. Including readily available olefins, this reaction has considerable advantages, such as mild conditions, broad substrate scope, and good functional group compatibility, making it desirable alternative traditional electrophile–nucleophile reactions.

Язык: Английский

Процитировано

169
Enantioselective C(sp3)–C(sp3) cross-coupling of non-activated alkyl electrophiles via nickel hydride catalysis DOI
Srikrishna Bera, Runze Mao, Xile Hu

и другие.

Nature Chemistry, Год журнала: 2020, Номер 13(3), С. 270 - 277

Опубликована: Дек. 30, 2020

Язык: Английский

Процитировано

168
Visible‐Light‐Promoted C(sp3)−H Alkylation by Intermolecular Charge Transfer: Preparation of Unnatural α‐Amino Acids and Late‐Stage Modification of Peptides DOI
Chao Wang,

Rupeng Qi,

Hongxiang Xue

и другие.

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(19), С. 7461 - 7466

Опубликована: Фев. 20, 2020

Disclosed herein is the visible-light-promoted deaminative C(sp3 )-H alkylation of glycine and peptides using Katritzky salts as electrophiles. Simple reaction conditions excellent functional-group tolerance provide a general strategy for efficient preparation unnatural α-amino acids precise modification with α-amino-acid residues. Mechanistic studies suggest that intermolecular charge transfer within glycine-Katritzky salt electron donor-acceptor (EDA) complex induces single-electron process without assistance photocatalyst.

Язык: Английский

Процитировано

161
N-Heterocyclic carbene-catalyzed deaminative cross-coupling of aldehydes with Katritzky pyridinium salts DOI Creative Commons
In‐Won Kim, Honggu Im, Hyeonyeong Lee

и другие.

Chemical Science, Год журнала: 2020, Номер 11(12), С. 3192 - 3197

Опубликована: Янв. 1, 2020

By employing an N-heterocyclic carbene (NHC) catalyst, we developed a versatile catalytic system that enables deaminative cross-coupling reactions of aldehydes with redox-active pyridinium salts.

Язык: Английский

Процитировано

156
Recent advances in nickel-catalyzed reductive hydroalkylation and hydroarylation of electronically unbiased alkenes DOI
Xiaoxu Wang, Xi Lu, Yan Li

и другие.

Science China Chemistry, Год журнала: 2020, Номер 63(11), С. 1586 - 1600

Опубликована: Сен. 28, 2020

Язык: Английский

Процитировано

154
NiH-Catalyzed Functionalization of Remote and Proximal Olefins: New Reactions and Innovative Strategies DOI
You Wang, Yuli He, Shaolin Zhu

и другие.

Accounts of Chemical Research, Год журнала: 2022, Номер 55(23), С. 3519 - 3536

Опубликована: Ноя. 9, 2022

Transition metal hydride catalyzed functionalization of remote and proximal olefins has many advantages over conventional cross-coupling reactions. It avoids the separate, prior generation stoichiometric amounts organometallic reagents use preformed reagents, which are sometimes hard to access may compromise functional group compatibility. The migratory insertion complexes generated in situ into readily available alkene starting materials, hydrometalation process, provides an attractive straightforward route alkyl intermediates, can undergo a variety sequential In particular, with synergistic combination chain-walking chemistry nickel, NiH-catalyzed undergone particularly intense development past few years. This Account aims chronicle progress made this arena terms activation modes, diverse functionalizations, chemo-, regio-, enantioselectivity.We first provide brief introduction general reaction mechanisms. Taking hydroarylation as example, four oxidation states Ni have allowed us develop two different strategies form final product: Ni(I)-H/X-Ni(II)-H platform that relies on reductants Ni(I/II/III) cycle redox-neutral or FG-Ni(II)-H reacts substrate forms products via Ni(0/II) pathway. We also demonstrate functionalization, including C-C bond-forming reactions more challenging C-N/C-S could be realized. Moreover, employment appropriate chiral ligands successfully realize corresponding asymmetric hydrofunctionalization olefins, hydroalkylation, hydroarylation, hydroalkenylation, hydroalkynylation, hydroamination. Interestingly, enantio-determining step enantioselective hydronickelation, selective oxidative addition, reductive elimination. To hydrofunctionalization, we developed ligand relay catalytic strategy simple ligands, for second coupling. novel design single, possibly structurally complex promote both steps success multicomponent convenient approach gain molecules. Finally, halides used olefin precursors cross-electrophile coupling Applications these discussed. hope will inspire future field overcome key challenges, conceptually new strategies, high-performance systems enhanced reactivity selectivity, cutting-edge catalyst design, further mechanistic studies.

Язык: Английский

Процитировано

147
Chiral Alkyl Amine Synthesis via Catalytic Enantioselective Hydroalkylation of Enecarbamates DOI
Deyun Qian, Srikrishna Bera, Xile Hu

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(4), С. 1959 - 1967

Опубликована: Янв. 22, 2021

Chiral alkyl amines are omnipresent as bioactive molecules and synthetic intermediates. The catalytic enantioselective synthesis of from readily accessible precursors is challenging. Here we develop a nickel-catalyzed hydroalkylation method to assemble wide range chiral enecarbamates (N-Cbz-protected enamines) halides with high regio- enantioselectivity. works for both nonactivated activated able produce enantiomerically enriched two minimally differentiated α-alkyl substituents. mild conditions lead functional group tolerance, which demonstrated in the postproduct functionalization many natural products drug molecules, well building blocks key intermediates compounds.

Язык: Английский

Процитировано

145
Streamlined Alkylation via Nickel-Hydride-Catalyzed Hydrocarbonation of Alkenes DOI
Zhikun Zhang, Srikrishna Bera, Chao Fan

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(16), С. 7015 - 7029

Опубликована: Апрель 12, 2022

Compounds rich in sp3-hybridized carbons are desirable drug discovery. Nickel-catalyzed hydrocarbonation of alkenes is a potentially efficient method to synthesize these compounds. By using abundant, readily available, and stable as pro-nucleophiles, reactions can have broad scope high functional group tolerance. However, this methodology still an early stage development, the first examples were reported only 2016. Herein, we summarize progress emerging field, with emphasis on enantioselective reactions. We highlight major developments, critically discuss wide range possible mechanisms, offer our perspective state challenges field. hope Perspective will stimulate future works area, making widely applicable organic synthesis.

Язык: Английский

Процитировано

131